CN101350405B - Positive electrode active materials for lithium secondary battery, method for preparing the same and lithium secondary battery - Google Patents

Positive electrode active materials for lithium secondary battery, method for preparing the same and lithium secondary battery Download PDF

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CN101350405B
CN101350405B CN2008101335223A CN200810133522A CN101350405B CN 101350405 B CN101350405 B CN 101350405B CN 2008101335223 A CN2008101335223 A CN 2008101335223A CN 200810133522 A CN200810133522 A CN 200810133522A CN 101350405 B CN101350405 B CN 101350405B
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ray diffraction
positive electrode
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secondary battery
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朴晸浚
宋守镐
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Samsung SDI Co Ltd
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention discloses a positive electrode active material for a lithium secondary battery, a method of preparing the same, and a lithium secondary battery comprising the same. The material is represented by the formulas: LiNi(1-x-y) CoxAlyO2 or LiNi(1-x-y)CoxMnyO2 (0.1<=x<=0.2 and 0.03<y<0.1), and whose X-ray diffraction peak intensity ratio I(2theta=45 degrees)/I(2theta=18 degrees) of an X-ray diffraction peak intensities found in the vicinity of an X-ray diffraction-scanning angle 2theta of about 45 degrees, to an X-ray diffraction peak intensity found in the vicinity of an X-ray diffraction-scanning angle 2theta of about 18 degrees, is in the range of from 46% to 51%. The positive electrode active material is fabricated by mixing Ni(1-x-y)CoxAlyO2 or Ni(1-x-y)CoxMnyO2 (0.1<= x<=0.2 and 0.03<y<0.1) with lithium hydrates (LiOH.H2O); and calcinating the mixture at a temperature of 750 DEG C, for more than 29 hrs, under an oxygen atmosphere.

Description

Secondary lithium batteries positive electrode active materials, its preparation method and lithium secondary battery
The cross reference of related application
The application number that the application requires to submit to Korea S Department of Intellectual Property on July 16th, 2007 is the korean patent application of 10-2007-0071105, and its disclosure is incorporated herein by reference.
Technical field
Each side of the present invention relates to a kind of lithium secondary battery, more specifically relates to positive electrode active materials, its preparation method that is used for lithium secondary battery and the lithium secondary battery that comprises this positive electrode active materials.
Background technology
Lithium secondary battery repeats to change lithium ion between positive pole and negative pole.Lithium secondary battery uses the material of embedding and de-embedding lithium ion as positive pole and negative active core-shell material.Usually, carbon class or metal (comprising metal oxide) carbon composite is as negative active core-shell material, and lithium-metal oxide is as positive electrode active materials.
Metallic cobalt is widely used as positive electrode active materials.In order to improve other characteristics, or for coping resources lacks, used other metals, for example Ni, Mn etc. (particularly transition metal) are as active material.Though use cobalt as positive electrode active materials in a large number, also use the lithium metal oxide of the metal composite that contains lithium and other metals.
Metal composite can be crystalline metal compound, for example LiMO 2, LiM 2O 4Deng, wherein M can be expressed as general formula Ni (1-x-y)Co xMn y(wherein x and y are the positive number less than 1, and 1-x-y is less than or equal to 1).
Cobalt acid lithium (LiCoO 2) have a stable charge, excellent electron conductivity and discharging voltage characteristic stably.But, because shortage, costliness and the toxicity of cobalt acid lithium are wished other material of exploitation.
Lithium nickelate (LiNiO 2) having the layer structure that is similar to cobalt acid lithium, discharge capacity is big, but is difficult to form simple layer structure.Owing to produce reactive Ni in the charging process 4+Ion, lithium nickelate are converted into the Li with rock salt structure xNi 1-xO, and discharge too much oxygen, this causes cycle life to descend and thermal instability.Nickel-cobalt class positive electrode active materials, for example LiNi that replaces a part of nickel with cobalt 1-xCo xO 2(wherein x=0.1～0.3) presents excellent charge/discharge and cycle life characteristics, but still has heat-labile problem.
On the other hand, the lithium metal oxide in the positive electrode active materials can form crystalline phase according to its formation method difference, or the crystalline phase and the amorphous phase of mixing.Even in crystalline phase, lithium metal oxide can form the mixture of two kinds of different crystal structures.This species diversity on the crystal structure causes in the cell reaction process difference on reactivity between active material and material around.
If positive electrode active materials participates in the different side reactions with electrolyte ingredient, according to different crystal structures, can form byproduct layer, for example solid electrolyte interface (SEI) layer at surface of positive electrode active material.Described byproduct layer has the ionic conductance different with electrolyte, thereby causes the variation of cell resistance.Because the generation of heat, the increase of cell resistance cause battery efficiency to reduce, battery functi on variation and cycle life reduce.
In the high-temperature storage test, nickel-cobalt class lithium ion battery stores 50 days at 60 ℃ under the condition that 4.2V charges fully.Compare before the high-temperature storage then and cell resistance afterwards.Like this comparison shows that before this test back resistance is elevated to test about 150% on.
Summary of the invention
The invention provides the positive electrode active materials that is used for lithium secondary battery, its preparation method, and the lithium secondary battery that comprises this positive electrode active materials.Described material has the high-temperature storage performance of improvement, and can suppress lithium secondary battery charging back because the side reaction that high-temperature storage causes.
According to an aspect of the present invention, provide a kind of be used for lithium secondary battery use general formula LiMO 2The positive electrode active materials of (wherein M is the metal composite that contains at least a transition metal) expression, this material has at least two kinds of crystalline phases.The strength ratio at the X-ray diffraction peak of the second stable crystalline phase is at least 46% under first crystalline phase of high temperatures and the low temperature.
According to each side of the present invention, the strength ratio at described X-ray diffraction peak can be 46%～51%.
According to each side of the present invention, described LiMO 2Can be LiNi (1-x-y)Co xAl yO 2Or LiNi (1-x-y)Co xMn yO 2(wherein 0.1≤x≤0.2 and 0.03＜y＜0.1).Described LiNi (1-x-y)Co xAl yO 2Can form by the following method: with the hydroxide (Ni of transition metal composite 0.8Co 0.15Al 0.05(OH) 2) mix with the crystal lithium hydroxide, then with described mixture 750 ℃ of calcination processing 29～40 hours.The strength ratio at the X-ray diffraction peak of 104 crystal structures and 003 crystal structure can be in 46%～51% scope.
According to a further aspect in the invention, provide a kind of positive electrode active materials that is used for the usefulness following general formula of lithium secondary battery: LiNi (1-x-y)Co xAl yO 2Or LiNi (1-x-y)Co xMn yO 2(wherein 0.1≤x≤0.2 and 0.03＜y＜0.1), and it is that about 45 ° X-ray diffraction peak intensity and X-ray diffraction-scanning angle 2 θ are the strength ratio I at the X-ray diffraction peak of about 18 ° X-ray diffraction peak intensity at X-ray diffraction-scanning angle 2 θ (2 θ=45 °)/ I (2 θ=18 °)Can be in 46%～51% scope.
According to each side of the present invention, the method that provides a kind of preparation to be used for the positive electrode active materials of lithium secondary battery, described method comprises: by stirring Ni (1-x-y)Co xAl y(OH) 2Or Ni (1-x-y)Co xMn y(OH) 2(wherein 0.1≤x≤0.2 and 0.03＜y＜0.1) and lithium hydroxide monohydrate (LiOHH 2O) mix, then with described mixture calcination processing 29～40 hours in 750 ℃ of following oxygen atmospheres.
According to each side of the present invention, a kind of lithium secondary battery is provided, comprising: electrode assemblie, it has the dividing plate between described positive plate of positive plate, negative plate and insertion and the negative plate; With the housing that holds described electrode assemblie.Described positive plate comprises the positive pole coating part that forms to the small part positive electrode collector surface by positive electrode active materials is coated in.Described positive electrode active materials can be used following general formula: LiNi (1-x-y)Co xAl yO 2Or LiNi (1-x-y)Co xMn yO 2(wherein 0.1≤x≤0.2 and 0.03＜y＜0.1).It is that about 45 ° X-ray diffraction peak intensity and X-ray diffraction-scanning angle 2 θ are the strength ratio I at the X-ray diffraction peak of about 18 ° X-ray diffraction peak intensity that described material has at X-ray diffraction-scanning angle 2 θ (2 θ=45 °)/ I (2 θ=18 °)Can be in 46%～51% scope.
According to each side of the present invention, described housing can comprise the jar with opening, and described electrode assemblie inserts wherein and seal the cap assemblies of described opening by this opening.Described housing can hold described electrode assemblie and electrolyte.
According to each side of the present invention, when described positive electrode active materials with nickel-cobalt metalloid compound, and aluminium or manganese is when preparing, the strength ratio at the X-ray diffraction peak of the second stable crystalline phase should be at least 46% under first crystalline phase of high temperatures and the low temperature.Described high temperature and low temperature are based on the high temperature that allows these two crystalline phase conversions, for example calcining heat.Described strength ratio increases along with the rising of calcining heat.
According to each side of the present invention, along with the rising of the crystal ratio of high temperatures, by with the reaction of additive agent electrolyte (even at high temperature (60 ℃) down in long term storage process) on the positive plate surface or the amount of the accessory substance that forms on the positive electrode active materials reduce.That is to say, even in the high-temperature storage process, also kept ionic conductance, thereby prevent the decline of charge/discharge efficient or cycle life.In order to improve aforementioned proportion, when the calcining source material formed described positive electrode active materials, with respect to conventional calcination time, calcination time had increased.
In the specification of back, will illustrate part of the present invention other aspect and/or advantage, and it can become obviously by explanation, is perhaps understood by practice of the present invention.
Description of drawings
By below in conjunction with the description of accompanying drawing to exemplary embodiment, these and/or other aspect of the present invention and advantage will be more obviously and easy to understand, wherein:
Fig. 1 is X-ray diffraction (XRD) spectrogram of exemplary embodiment, and wherein the X-axle is represented the scanning angle scope between incidence angle and the angle of reflection, and the Y-axle is represented diffracted ray intensity;
The X-ray diffraction spectrogram of the peak intensity of the concrete diffracted ray of explanation that Fig. 2 obtains for the diffracted ray by 104 type crystal in the enlarged drawing 1;
Fig. 3 is according to exemplary embodiment and Comparative Examples, to the proportionate relationship figure of 104 types under each calcination time and 003 type crystal X-ray diffraction peak intensity; With
Fig. 4 is according to exemplary embodiment and Comparative Examples, and resistance increases than the figure with respect to calcination time in the high-temperature storage process.
Embodiment
Now in detail with reference to exemplary embodiment of the present invention, the example in conjunction with the accompanying drawings, the identical reference numbers designate components identical of using in the whole text wherein.Below with reference to these exemplary embodiments of these description of drawings, to explain each side of the present invention.
The calcining of source material
According to each side of the present invention, described positive electrode active materials can form by mixing and calcining source material.Though method for calcinating can change according to the composition of metal composite (M) is different, heating is carried out at 700 ℃～900 ℃ usually.For too high temperature, the battery behavior of positive electrode active materials tends to variation.For low excessively temperature, be difficult to obtain equably desired composition.Calcining is carried out under stationary temperature and time usually.Can implement calcining to remove moisture content by under temperature, preheating source material than low 300～400 ℃ of calcining heat.With certain speed described source material is heated to calcining heat then, to prevent anxious heat.Each side of the present invention can further comprise anneals source material under the temperature than low 100～200 ℃ of calcining heat.Described calcining is carried out in the oxidizing atmosphere of the oxygen that contains high-load usually.
Described positive electrode active materials can prepare by following steps: form particulate lithium metal oxide (LiMO 2), described lithium metal oxide is that the nickel-cobalt metalloid compound of major metal is made with nickel by what added particulate aluminium or manganese source material, in solvent, evenly mixes then, and 750 ℃ of calcinings down.Usually, the material that forms oxide is used as source material oxide or when calcining.
The hydroxide of lithium and nitrate are widely used as the lithium source material.The oxide of nickel or cobalt, hydroxide or nitrate are usually as nickel source material and cobalt source material.The hydroxide of the nickel-cobalt that obtains from reaction crystallizing method can be used for improving the efficient of positive electrode active materials by the even mixing of nickel and cobalt.The oxide of aluminium, hydroxide or nitrate are as the aluminium source material.
The lithium content of lithium metal oxide is a benchmark with 1 mole, but can contain 20% wide-ultra crosses 1 mole amount (that is, 1 mole to 1.2 moles).The lithium content that reduces has increased the formation of crystal in the positive electrode active materials, causes the decline of cell charging capacity.On the contrary, in the forming process of positive electrode active materials, too much lithium content has destroyed the conversion of source materials such as lithium carbonate to lithium metal oxide, and lithium carbonate or lithium hydroxide may be precipitated out from positive electrode active materials.
The content range of cobalt is 0.1～0.2 mole, and this makes the metal composite of nickel and cobalt have good thermal stability and charging.
When with respect to 1 mole of lithium, when nickel-cobalt metalloid compound contained the aluminium of 0.03～0.1 mol ratio, described metal composite had the diffusivity of improvement for the lithium ion in positive electrode active materials.So this is beneficial in the application in the battery of electrodynamic instrument or the output of the height hybrid power automobile battery battery.The adding of aluminium helps the metal composite of nickel and cobalt to have stable crystal structure in charging process.So when containing aluminium in the described metal composite, even in hot environment, the crystal structure that positive electrode active materials also keeps relative stability, thus prevented the decline of capacity.But, because aluminium itself for not very big contribution of charging, has adverse effect so generally contain when surpassing 0.1 mole aluminium.
When the metal composite based on nickel and cobalt further contains manganese, can improve the thermal stability of positive electrode active materials.When the content range of manganese is during from trace to 0.3 mole of manganese of every mole of lithium for example, it can improve thermal stability and fail safe.If the content of manganese surpasses 0.3 mole, the thermal stability of positive electrode active materials can increase, but its charge can descend.
Fig. 1 illustrates X-ray diffraction (XRD) spectrogram of an exemplary embodiment, specifically is 003 and 104 type crystal structure peaks; Fig. 2 shows the X-ray diffraction spectrogram of peak intensity of 104 type crystal structure of key diagram 1.Fig. 3 shows the strength ratio according to the X-ray diffraction peak of the positive electrode active materials of exemplary embodiment and Comparative Examples; Fig. 4 then shows the increase of resistance of the lithium secondary battery of the positive electrode active materials that uses described exemplary embodiment and Comparative Examples.The increase of the ratio at the X-ray diffraction peak of two crystal structures of the positive electrode active materials of following table 1 illustrated example embodiment and Comparative Examples and the internal resistance that in high-temperature storage test, records.
Reference table 1, Fig. 3 and Fig. 4, in exemplary embodiment 1～3, the strength ratio at the X-ray diffraction peak of relative 003 crystal structure of 104 crystal structures is in 46%～51% scope.And behind high temperature storage, resistance increases than being greater than 138% when calcination time is 30 hours, is 135% in the time of 35 hours, is 137% in the time of 40 hours, but all less than 140%.
Compare with exemplary embodiment, Comparative Examples shows that the strength ratio at the X-ray diffraction peak of relative 003 crystal structure of 104 crystal structures when calcination time is 20 or 25 hours is respectively about 43%, 44% and 45%, comprises about 42%.For the calcining sample, behind high temperature storage, resistance increases than being respectively 158% and 149%, all greater than 140%.140% to be benchmark, the maximum that shows saturation condition is described, corresponding calcination time is about 29 hours.The increase of internal resistance slowly reduces, even under relatively low calcination time, thereby has the effect that reduces the internal resistance increase.But, consider the calcination time of increase and the reduction of corresponding efficient, the 140%th, suitable.
LiOHH 2O and Ni 0.8Co 0.15Al 0.05(OH) 2Mixing molar ratio is 1.03: 1, to obtain described exemplary embodiment and Comparative Examples.
[table 1]
Embodiment Positive electrode active materials Calcining heat Calcination time The diffracted ray peak intensity compares I (104)/I (003) Resistance increases than (Δ R) after the high-temperature storage
Comparative Examples 1 LiOH·H 2O+ Ni 0.8Co 0.15Al 0.05(OH) 2 750℃ 20 hours 42.8％ 42.2％ 42.9％ 158％
Comparative Examples 2 LiOH·H 2O+ Ni 0.8Co 0.15Al 0.05(OH) 2 750℃ 25 hours 43.7％ 44.6％ 44.3％ 149％
Embodiment 1 LiOH·H 2O+ Ni 0.8Co 0.15Al 0.05(OH) 2 750℃ 30 hours 47.8％ 49.1％ 49.1％ 138％
Embodiment 2 LiOH·H 2O+ Ni 0.8Co 0.15Al 0.05(OH) 2 750℃ 35 hours 48.3％ 49.0％ 48.7％ 135％
Embodiment 3 LiOH·H 2O+ Ni 0.8Co 0.15Al 0.05(OH) 2 750℃ 40 hours 48.9％ 49.6％ 48.1％ 137％
Further illustrate in greater detail each side of the present invention below with reference to concrete exemplary embodiment and Comparative Examples.What however, it should be understood that is that the present invention is not limited to these concrete exemplary embodiments.
Exemplary embodiment 1:
With 1.03: 1 ratios with lithium hydroxide monohydrate (LiOHH 2O) with the hydroxide (Ni of transition metal composite 0.8Co 0.15Al 0.05(OH) 2) mix, and calcined 30 hours down at 750 ℃, to obtain three nickel-cobalt class lithium metal oxide (LiNi that contain trace Al 0.8Co 0.15Al 0.05O 2) sample.
These samples are put into X-ray diffractometer, and the strength ratio that records the X-ray diffraction peak of 104 crystal structures and 003 crystal structure then is respectively 47.8%, 49.1% and 49.1%.The results are shown in table 1.
Then, these samples are used as the positive electrode active materials in the lithium secondary battery, and described battery is in constant current/constant voltage (CC-CV) charging down.Initial charge is carried out under the constant current of 4A, charges to continuing under constant voltage behind the voltage that arrives 4.2V then.Afterwards, when electric current drops to the cut-off current of 100mA, stop charging.Charged lithium secondary battery wore out 50 days at 60 ℃, detected the D.C. resistance of these batteries then.
Lithium secondary battery with as above identical method preparation charges under 4A constant current and 4.2V constant voltage, stops charging when the cut-off current of 100mA, and charging suspends 2 hours then.Measure the direct current resistance of inside battery then.
Described lithium secondary battery can comprise forming positive plate, negative plate and dividing plate according to conventional preparation method's preparation; They are stacked or stacked and reel and to prepare electrode assemblie; Described electrode assemblie is inserted in the housing; Seal described housing then.Electrode contact is connected on described positive plate and the negative plate.Each battery lead plate can comprise the electrode coating part that forms by coated electrode active material on electrode collector.The coating of described positive electrode active materials can comprise that the slip that will contain described positive electrode active materials is coated on the surface of positive electrode collector, and is dry then.
Described housing can be bag or jar, and cap assemblies.Described electrode assemblie is inserted in the opening of described jar or bag, and can inject the electrolyte into wherein, and/or is included in wherein with the formation of solid electrolyte dividing plate.
D.C. resistance with under the state after at high temperature aging direct current resistance is afterwards charged down divided by normal temperature multiply by 100% then, obtains described resistance and increases than (Δ R).Resulting mean value is 138%.
The direct current resistance is meant in 10A discharge 10 seconds, 1A discharge 10 seconds, 10A discharge 4 seconds then, simultaneously 18 seconds and 23 seconds measuring voltages after beginning to discharge; Obtain divided by 9A with the survey voltage difference.
Adopt the X-ray diffractometer of copper-potassium (CuK) α-ray to be used for Analysis of X-x ray diffraction.For example, can use D8 ADVANCE diffractometer (Bruker company).
Diffraction conditions are as follows: generator is set to 40kV/30mA; 15 °～70 ° of sweep limitss; 0.04 ° of step-length; Continuous sweep; Per 1.00 seconds sweep times of step/step; 1 ° of divergent slit receives slit 0.1mm.
Exemplary embodiment 2:
In exemplary embodiment 2, repeat the process of exemplary embodiment 1, difference is that calcining was carried out 35 hours at 750 ℃.Each sample is put into X-ray diffractometer, measure the strength ratio I at the X-ray diffraction peak of 104 crystal structures and 003 crystal structure then (104)/ I (003), obtain 48.3%, 49.0% and 48.7% result respectively.
Constitute the lithium secondary battery that comprises these positive electrode active materials then.Measure 60 ℃ before aging 50 days/afterwards internal resistance.The mean value that resistance increases than (Δ R) is 135%.
Exemplary embodiment 3:
Repeat the process of exemplary embodiment 1, difference is that calcining was carried out 40 hours at 750 ℃.Each sample is put into X-ray diffractometer, measure the strength ratio I at the X-ray diffraction peak of 104 crystal structures and 003 crystal structure then (104)/ I (003), obtaining 48.9%, 49.6% and 48.1% result respectively, the result under the calcination time (35 hours) of these results and exemplary embodiment 2 compares and does not produce any effective difference.
Constitute lithium secondary battery with these positive electrode active materials then.Measure 60 ℃ before aging 50 days/afterwards internal resistance, record 137% resistance and increase ratio.Resistance during the calcination processing of this explanation with respect to 35 hours increases than having increased.
But such difference is very little, is not considered to significant difference,, does not show that resistance increases than actual increase is arranged that is.Specifically, even surpassing under 35 hours the calcination time condition, resistance increases than also not changing.
So, be that 750 ℃ calcining heat is enough under 30～40 hours the condition at calcination time.Surpass this scope, heat treated cost and time-related production cost increase, thereby cause lower productivity ratio.
Comparative Examples 1:
Repeat the process of exemplary embodiment 1, difference is that calcining was carried out 20 hours at 750 ℃.Sample is put into X-ray diffractometer, measure the strength ratio I at the X-ray diffraction peak of 104 crystal structures and 003 crystal structure then (104)/ I (003), obtain 42.8%, 42.2% and 42.9% result respectively.
Structure comprises with the lithium secondary battery of these samples as positive electrode active materials then.Measure 60 ℃ before aging 50 days/afterwards internal resistance, recording the mean value that resistance increases than (Δ R) is 158%.
Comparative Examples 2:
Repeat the process of exemplary embodiment 1, difference is that calcining was carried out 25 hours at 750 ℃.Each sample is put into X-ray diffractometer, measure the intensity I at the X-ray diffraction peak of 104 crystal structures and 003 crystal structure then (104)/ I (003), obtain 43.7%, 44.6% and 44.3% result respectively.
Structure comprises with the lithium secondary battery of these samples as positive electrode active materials then.Measure 60 ℃ before aging 50 days/afterwards internal resistance, recording the mean value that resistance increases than (Δ R) is 149%.
In sum, according to each side of the present invention, in lithium metal oxide, under HTHP,, can change by the formation condition that changes described positive electrode active materials with the crystalline component of the positive electrode active materials of electrolyte generation side reaction with nickel-cobalt metalloid compound.So in the high-temperature charging process, each side of the present invention can advantageously reduce the rate of rise of the internal resistance of lithium secondary battery, and can prevent the battery performance variation, thereby improves the cycle life of battery.
Though shown and several exemplary embodiment of the present invention be described, but it will be understood by those skilled in the art that and to change and do not deviate from principle of the present invention and spirit these exemplary embodiments that scope of the present invention is limited by claims and equivalent thereof.

Claims (6)

1. a positive electrode active materials that is used for lithium secondary battery comprises with general formula LiNi (1-x-y)Co xAl yO 2The lithiumation metal oxide of expression, 0.1≤x≤0.2 and 0.03＜y＜0.1 wherein, wherein:
Described lithiumation metal oxide has first crystalline phase and second crystalline phase;
It is 104 about 45 ° crystal structures at X-ray diffraction-scanning angle 2 θ that described first crystalline phase has the X-ray diffraction peak;
It is 003 about 18 ° crystal structure at X-ray diffraction-scanning angle 2 θ that described second crystalline phase has the X-ray diffraction peak;
The strength ratio at the X-ray diffraction peak of first crystalline phase and second crystalline phase is 46%～51%, and
Described X-ray diffraction peak adopts copper-potassium (CuK) α-ray emission body to obtain.
2. positive electrode active materials as claimed in claim 1, wherein said by general formula LiNi (1-x-y)Co xAl yO 2The lithiumation metal oxide of expression forms by the following method:
With Ni 0.8Co 0.15Al 0.05(OH) 2With crystal lithium hydroxide monohydrate LiOHH 2O mixes; With
Calcined described mixture 29～40 hours down at 750 ℃.
3. lithium secondary battery comprises:
Electrode assemblie has the dividing plate between described positive plate of positive plate, negative plate and insertion and the negative plate; With
Be used to hold the housing of described electrode assemblie,
Wherein said positive plate comprises the positive electrode collector that is coated with positive electrode active materials as claimed in claim 1 or 2.
4. lithium secondary battery as claimed in claim 3, wherein said housing comprises:
Jar with opening, described electrode assemblie inserts wherein by this opening; With
Seal the cap assemblies of described opening.
5. method for preparing the positive electrode active materials that is used for lithium secondary battery, described method comprises:
Will be by general formula Ni (1-x-y)Co xAl y(OH) 2The hydroxide and the lithium hydroxide monohydrate LiOHH of the transition metal composite of expression 2O mixes, wherein 0.1≤x≤0.2 and 0.03＜y＜0.1; With
Calcine described mixture, forming described positive electrode active materials,
The strength ratio I (104) at first crystalline phase of wherein said positive electrode active materials and the X-ray diffraction peak of second crystalline phase/I (003) in 46%～51% scope,
It is 104 about 45 ° crystal structures at X-ray diffraction-scanning angle 2 θ that described first crystalline phase has the X-ray diffraction peak,
It is 003 about 18 ° crystal structure at X-ray diffraction-scanning angle 2 θ that described second crystalline phase has the X-ray diffraction peak,
Described calcining is included under 700～900 ℃ the temperature, in the oxygen atmosphere, heats described mixture 29～40 hours.
6. method as claimed in claim 5, wherein said calcining are included under 750 ℃ the temperature, in the oxygen atmosphere, heat described mixture 29～40 hours.
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